By Rogerio Jelymayer And Paul Kiernan 

SÃO PAULO--Brazil's Federal Police said they arrested the chief executives of construction giants Odebrecht SA and Andrade Gutierrez on Friday morning, in the latest phase of the continuing investigation into what prosecutors and the police allege was a corruption scheme involving contracts signed by state run oil company Petróleo Brasileiro SA, or Petrobras.

The arrests mark the first time executives from Odebrecht, one of Latin America's biggest construction firms, and Andrade Gutierrez have been arrested. Both companies previously had been named in the investigation, but no executives had been arrested.

Marcelo Odebrecht and Otavio Azevedo, the chief executives of Odebrecht and Andrade Gutierrez, respectively, were among those arrested Friday, according to a police spokesman. The executives are accused of participating in the formation of cartels, money laundering and corruption, the police spokesman said.

"We have no doubt that Odebrecht and Andrade Gutierrez headed the cartel scheme within Petrobras," said Brazilian federal prosecutor Carlos Fernando dos Santos Lima. "I do not see how the companies can claim innocence given how much evidence we have."

Mr. Lima said executives from the two companies had not been arrested earlier because, he alleged, they "had a more sophisticated system" for making the alleged bribe payments, using foreign bank accounts in Switzerland, Monaco and Panama.

The lawyer for Odebrecht declined to comment for this article, and a spokeswoman for Andrade Gutierrez declined to provide the name of the company's lawyer. The company said in a short note that it is cooperating with the investigation, and denied any wrongdoing. Attempts to contact the executives or their lawyers weren't immediately successful Friday.

In a statement, Odebrecht said that its offices in São Paulo and Rio de Janeiro were searched by police, but it didn't confirm the arrests. The company said that the police operation was unnecessary, since the company is cooperating with the authorities' investigation. Odebrecht officials have previously denied any involvement in the alleged scheme.

The arrests are part of the continuing investigation into what prosecutors have dubbed Operation Car Wash, in which Petrobras, along with Brazil's biggest construction firms and about 50 current and former politicians are alleged to have participated in a yearslong bribery scheme. Investigators accuse Petrobras officials of taking a cut of cash from inflated contracts and funneling the rest to lawmakers and political parties. Some of the accused have admitted wrongdoing in exchange for lesser punishment, according to prosecutors, while others have denied involvement and await trial.

Prosecutors said in May that the total estimated amount alleged to have been paid in bribes was $2 billion. In April, Petrobras wrote off $2.1 billion due to alleged corruption and more than $14 billion for overvalued assets.

Write to Paul Kiernan at paul.kiernan@wsj.com

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